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Recently, the mapping approach to surface hopping (MASH) was proposed as a method to simulate the non-adiabatic dynamics of two-level systems. It was shown that the method possesses many desirable qualities, both theoretically and through…

Chemical Physics · Physics 2025-07-08 Jan Vavřín

We present a nonadiabatic classical-trajectory approach that offers the best of both worlds between fewest-switches surface hopping (FSSH) and quasiclassical mapping dynamics. This mapping approach to surface hopping (MASH) propagates the…

Chemical Physics · Physics 2023-03-29 Jonathan R. Mannouch , Jeremy O. Richardson

Nonadiabatic dynamics methods are an essential tool for investigating photochemical processes. In the context of employing first principles electronic structure techniques, such simulations can be carried out in a practical manner using…

Chemical Physics · Physics 2024-05-08 Jonathan R. Mannouch , Aaron Kelly

In this work, we describe various improved implementations of the mapping approach to surface hopping (MASH) for simulating nonadiabatic dynamics. These include time-reversible and piecewise-continuous integrators, which is only formally…

Chemical Physics · Physics 2026-03-31 J. Amira Geuther , Kasra Asnaashari , Jeremy O. Richardson

We describe a multiple electronic state adaptation of the mapping approach to surface hopping introduced recently by Mannouch and Richardson (J. Chem. Phys. 158, 104111 (2023)). This adaptation treats populations and coherences on an equal…

Chemical Physics · Physics 2024-01-10 Johan E. Runeson , David E. Manolopoulos

It is well known that fewest-switches surface hopping (FSSH) fails to correctly capture the quadratic scaling of rate constants with diabatic coupling in the weak-coupling limit, as expected from Fermi's golden rule and Marcus theory. To…

Chemical Physics · Physics 2023-11-16 Joseph E. Lawrence , Jonathan R. Mannouch , Jeremy O. Richardson

In response to a community prediction challenge, we simulate the nonadiabatic dynamics of cyclobutanone using the mapping approach to surface hopping (MASH). We consider the first 500 fs of relaxation following photo-excitation to the S2…

In this work, we employ trajectory-based simulations to predict the electronic coherences created by nonadiabatic dynamics near conical intersections. The mapping approach to surface hopping (MASH) is compared with standard fewest-switches…

Chemical Physics · Physics 2025-05-09 Daniele Furlanetto , Jeremy O. Richardson

The violation of detailed balance poses a serious problem for the majority of current quasiclassical methods for simulating nonadiabatic dynamics. In order to analyze the severity of the problem, we predict the long-time limits of the…

Quantum Physics · Physics 2023-11-20 Graziano Amati , Jonathan R. Mannouch , Jeremy O. Richardson

In mixed quantum-classical simulations of molecule-metal surface interactions, the discretization of the metallic electronic continuum typically results in a closed-system representation that fails to capture the open-system nature of the…

Chemical Physics · Physics 2026-03-19 Yongtao Ma , Wenjie Dou

We propose a method which combines the quantum-classical mapping approach to surface hopping (MASH) with the dissipative quantum dynamics of the Lindblad master equation. Like conventional surface-hopping methods, our approach is based on…

Quantum Physics · Physics 2026-03-31 Kasra Asnaashari , Jeremy O. Richardson

Rare nonadiabatic events play a central role in photochemistry but remain difficult to simulate because excited-state dynamics is computationally demanding and often stochastic. Here we introduce a deterministic and time-reversible…

We describe how to simulate charge diffusion in organic semiconductors using a recently introduced mixed quantum-classical method, the mapping approach to surface hopping (MASH). In contrast to standard fewest-switches surface hopping, this…

Chemical Physics · Physics 2024-10-01 Johan E. Runeson , Thomas J. G. Drayton , David E. Manolopoulos

A surface-hopping algorithm recently derived from the exact factorization approach, SHXF, [Ha, Lee, Min, J. Phys. Chem. Lett. 9, 1097 (2018)] introduces an additional term in the electronic equation of surface-hopping, which couples…

Chemical Physics · Physics 2022-02-08 Patricia Vindel-Zandbergen , Spiridoula Matsika , Neepa T. Maitra

Surface hopping algorithms, as an important class of quantum dynamics simulation algorithms for non-adiabatic dynamics, are typically performed in the adiabatic representation, which can break down in the presence of ill-defined adiabatic…

Numerical Analysis · Mathematics 2022-05-06 Zhenning Cai , Di Fang , Jianfeng Lu

In the spirit of the fewest switches surface hopping, the frozen Gaussian approximation with surface hopping (FGA-SH) method samples a path integral representation of the non-adiabatic dynamics in the semiclassical regime. An improved…

Chemical Physics · Physics 2016-10-12 Jianfeng Lu , Zhennan Zhou

Interest in vibrational polaritonic chemistry, where ground-state chemical kinetics are modified via confined optical modes in a cavity, has surged in recent years. Although models have been developed to understand cavity-modified…

Quantum Physics · Physics 2025-02-10 Muhammad R. Hasyim , Arkajit Mandal , David R. Reichman

The powerful molecular dynamics (MD) simulation is basically based on a picture that the atoms experience classical-like trajectories under the exertion of classical force field determined by the quantum mechanically solved electronic…

Chemical Physics · Physics 2013-12-16 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang

Rare nonadiabatic reactions are a key component of many important molecular processes but are challenging to capture with direct dynamical simulations. In this paper, we combine our recently developed mapping approach to surface hopping…

Chemical Physics · Physics 2026-03-19 Danial Ghamari , Jeremy O. Richardson

Accurate simulation the many-electronic nonadiabatic dynamics process at metal surfaces remains as a significant task. In this work, we present an orbital surface hopping (OSH) algorithm rigorously derived from the orbital quantum classical…

Chemical Physics · Physics 2025-11-24 Yong-Tao Ma , Rui-Hao Bi , Wenjie Dou
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